Serine compounds, their preparation and their use in cosmetic or dermatological compositions

ABSTRACT

At least one serine compound corresponding to the Formula I: ##STR1## in which R and R&#39;, which are identical or different, represent a linear or branched hydrocarbon radical having from 8 to 30 carbon atoms, or the D-optical isomer of Formula I, the L-optical isomer of Formula I, or a non-racemic mixture of at least two of the optical isomers; the preparation of these compounds and their use, especially in cosmetic or pharmaceutical compositions intended for treating or caring for the hair or for the skin.

This is a divisional of application Ser. No. 08/437,809, filed May 9,1995, now U.S. Pat. No. 5,626,855.

The subject of the invention is new serine derivatives and theirpreparation. Another subject of the invention is cosmetic ordermatological compositions containing these new derivatives.

Serine is an amino acid which is important for the hair and for the skinbecause it is a precursor of ceramides, which are compounds of thestratum corneum of the epidermis and of the hair and are consideredessential by their barrier properties which prevent, for example,problems of water permeability.

Known serine derivatives, as exemplified in Patent ApplicationEP-A-0,408,448, the disclosure of which is hereby incorporated byreference, include lipoamino acids containing a urethane functionalgroup. These are ionic compounds with a single chain which form part ofcosmetic or dermatological compositions for skin treatment and whichgive excellent results on dry skins.

The inventor has found new serine compounds which have at least the sameproperties for the skin as those described in Patent ApplicationEP-A-0,408,448 but which additionally are of great advantage in hairtreatment as a disentangling or smoothing agent.

The subject of the invention is therefore serine compounds orderivatives which correspond to the formula: ##STR2## wherein R and R',which are identical or different, represent a linear or branchedhydrocarbon radical having from 8 to 30 carbon atoms. The invention isdrawn to at least one racemic mixture of a serine compound of formula(I), the D-optical isomer of formula (I), the L-optical isomer offormula (I), or a non-racemic mixture of at least two of the opticalisomers.

Hydrocarbon radical is understood to mean any saturated or unsaturatedhydrocarbon radical having from 8 to 30 carbon atoms.

According to a preferential embodiment of the invention, R and R', whichare identical or different, are saturated radicals or radicals whichcontain a double bond.

According to another embodiment of the invention, R and R', which areidentical or different, preferably contain from 8 to 18 carbon atoms.

Mention may be made, as compounds of formula (I), of:

dodecyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate,

octyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate,

hexadecyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate,

dodecyl 3-hydroxy-2- N-(2-ethylhexyloxycarbonyl)amino!propionate,

octyl 3-hydroxy-2- N-(2-ethylhexyloxycarbonyl)amino!propionate,

hexadecyl 3-hydroxy-2- N-(2-ethylhexyloxycarbonyl)amino!propionate,

dodecyl 3-hydroxy-2- N-(dodecyloxycarbonyl)amino!propionate,

octyl 3-hydroxy-2- N-(dodecyloxycarbonyl)amino!propionate,

hexadecyl 3-hydroxy-2- N-(dodecyloxycarbonyl)amino!propionate,

dodecyl 3-hydroxy-2- N-(oleyloxycarbonyl)amino!propionate,

octyl 3-hydroxy-2- N-(oleyloxycarbonyl)amino!propionate,

hexadecyl 3-hydroxy-2- N-(oleyloxycarbonyl)amino!propionate.

The following are particularly preferred among the above compounds:

dodecyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate,

octyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate, and

hexadecyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate.

The present invention is also drawn to a process for the preparation ofthe compounds of formula (I) as defined above. According to thisprocess, an N-liposerine salt corresponding to the formula: ##STR3## andan activated hydrocarbon derivative corresponding to the formula:

    R'X                                                        (III)

in which R and R', which are identical or different, represent a linearor branched hydrocarbon radical having from 8 to 30 carbon atoms;

Q⁺ is an organic or inorganic cation;

and X an activating group, are reacted in the presence of a phasetransfer agent.

According to a preferential embodiment of the invention, R and R', whichare identical or different, are saturated radicals or radicals whichcontain a double bond.

According to another embodiment of the invention, R and R', which areidentical or different, preferably contain from 8 to 18 carbon atoms.

Mention may be made, as Q⁺ cation example, of alkali metal cations suchas potassium.

The X activating group can be a halogen atom or a mesyloxy, brosyloxy ortosyloxy radical.

It is possible to use, as phase transfer agent, any compound commonlyused in this type of reaction. A solid/liquid phase transfer agent ispreferentially used. A quaternary ammonium derivative, such as, forexample, trioctylmethylammonium chloride, is preferably used.

The liposerine salts used in this process are, for example, the salts ofthe compounds cited in Patent Application EP-A-0,408,448, such as thesalts of N-(hexadecyloxycarbonyl)serine,N-(2-ethylhexyloxycarbonyl)serine or N-(dodecyloxycarbonyl)serine. Thesecan also be the salts of N-(oleyloxycarbonyl)serine.

The liposerine salts used can be provided in the form of their D or Lisomers or of a mixture of these forms. In other words, beginning witheither a D- or L- optical isomer of formula (II), the respective D- orL- optical isomer of formula (I) can be obtained. Alternatively, aracemic mixture of formula (II) can be used to prepare a racemic mixtureof formula (I) followed by conventional separation of the mixture intothe respective D- or L- optical isomers.

According to a first embodiment of the process of the invention, (A),the phase transfer reaction generally takes place at a temperature above20° C., preferably from 60° C. to 180° C. and more preferably from 80°C. to 120° C. The duration of the reaction is then generally greaterthan 2 hours, preferably from 2 to 15 hours and more preferably from 4to 10 hours.

According to a second embodiment of the process according to theinvention, (B), the phase transfer reaction can take place by subjectingthe reaction mixture, in the chamber of a microwave oven, to a nominalpower generally greater than 100 watts for a reaction time generally of1 to 15 minutes and preferably from 2 to 7 minutes.

Whatever the method of preparation used, (A or B), the molar ratio ofthe compound of formula (III) to the compound of formula (II) isgenerally from 1 to 5, and preferably from 1.2 to 2.

The phase transfer agent is, in the reaction mixture, whatever theprocedure used, in a proportion of generally from 0.1% to 10%, andpreferably from 0.5% to 5%, by weight with respect to the weight ofcompound of formula (I).

Once the reaction is complete, the salts can be removed by washing withwater. The ester thus obtained is then purified and characterizedaccording to techniques known to those skilled in the art.

The present invention is further drawn to cosmetic or dermatologicalcompositions containing at least one racemic mixture of a serinecompound, the D- optical isomer, the L- optical isomer, or thenon-racemic mixture corresponding to the formula (I).

In the compositions according to the invention, the compounds of formula(I) are generally present at a concentration which can range from 0.05%to 20%, and preferably from 0.5% to 10%, by weight with respect to thetotal weight of the composition.

These compositions contain the ingredients commonly used in cosmeticsfor this type of preparation. Thus, they can contain at least oneadditive chosen from fatty alcohols, thickeners, fatty acid esters,esters of fatty acids and glycerol, silicones (volatile or nonvolatile,functionalized or nonfunctionalized), surface-active agents, fragrances,preservatives, sunscreens, proteins, vitamins, polymers, organic orinorganic oils and any other additive conventionally used in thecosmetics field.

The compositions of the invention can also be provided in any,optionally vesicular, solution or dispersion form of the derivatives asdefined above.

All these compositions are prepared according to the usual methods knownto those skilled in the art.

A fourth subject of the invention relates to the use of a composition asdefined above in treating and/or caring for the hair or for the skin.

A fifth subject of the invention relates to a process for cosmetictreatment, in which a composition as defined above is used, intendedespecially for improving smoothing and/or disentangling of hair.

A sixth subject of the invention relates to a process for cosmetic ordermatological treatment, in which a composition as defined above isused, intended for treating the skin.

Examples of the preparation of serine compounds or derivativescorresponding to the formula (I), as well as examples of compositionscontaining them, will now be given, by way of illustration. Theseexamples should in no way limit the scope of the invention.

EXAMPLE 1

Preparation of dodecyl 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate:

The experimental method referenced B in the text was used for thispreparation.

The following were introduced into a 30 ml crystallized dish:

4.86 mmol (2 g) of potassium 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate,

9.72 mmol (2.32 ml) of bromododecane,

0.04 g of trioctylmethylammonium chloride.

The mixture was irradiated for 3 minutes in a microwave oven (MenuMasters 3100i, 2450 Mz, nominal power 1400 watts).

After cooling, a beige wax was obtained which was dissolved atapproximately 40° C. in8 ml of methanol per gram of wax. An insolublewhite material (potassium bromide) remained and was removed by filteringoff.

The filtrates were cooled to 4° C. A white precipitate appeared whichwas collected by filtering off and then dried.

The weight obtained was 1.8 g for 2.63 g expected, i.e. a yield of 68%.

White-coloured crystals were obtained, the characteristics of whichwere:

Melting point (obtained by Mettler FP 89): M.p.=65° C.(solvent=methanol)

Elemental analysis: C₃₂ H₆₃ NO₅ -1.5H₂ O, M.W.=569

    ______________________________________                                                    C         H      N                                                ______________________________________                                        Calculated    67.56       11.69  2.46                                         Theory (+ 1.5 H.sub.2 O)                                                                    67.88       10.97  2.37                                         ______________________________________                                    

¹³ C NMR: conformed to the expected structure.

EXAMPLE 2

Preparation of octyl 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate.

The preparation was carried out as in Example 1, according to Process B,by mixing:

4.86 mmol (2 g) of potassium 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate,

9.72 mmol (1.68 ml) of bromooctane,

0.04 g of trioctylmethylammonium chloride.

An amber liquid was obtained, which congealed on cooling, which wasdissolved at approximately 40° C. in 7 ml of methanol per gram ofproduct. A white insoluble material (potassium bromide) remained and wasremoved by filtering off.

The filtrates were cooled to 4° C. A white precipitate appeared whichwas collected by filtering off and then dried.

The weight obtained was 1.2 g for 2.36 g expected, i.e. a yield of 50%.

The characteristics of the product were:

Melting point (obtained by Mettler FP 89): M.p.=55° C.(solvent=methanol)

Elemental analysis: C₂₈ H₅₅ NO₅ -1.5H₂ O, M.W.=513

    ______________________________________                                                    C         H      N                                                ______________________________________                                        Calculated    65.59       11.4   2.73                                         Theory (+ 1.5 H.sub.2 O)                                                                    65.50       10.77  2.92                                         ______________________________________                                    

¹³ C NMR: conformed to the expected structure.

EXAMPLE 3

Preparation of hexadecyl 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate

This product was obtained according to Process A.

The following were introduced into a 500 ml round-bottomed flaskequipped with a stirrer, a thermometer and a vertical reflux condenser:

27 mmol (10 g) of 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propanoicacid,

27 mmol (3 g) of potassium tert-butoxide,

100 ml of dimethylformamide.

The reaction mixture was maintained at 20° C. with stirring for 1 hour.

The following were then added:

200 ml of N-methylpyrrolidone.

27 mmol of hexadecyl bromide (8.2 g).

The reaction mixture was heated at 80° C. for 21/2 hours.

The solvents were removed under reduced pressure.

The residue obtained was taken up in 120 ml of ethyl acetate and 120 mlof water.

Two phases and a precipitate were obtained. The precipitate wascollected by filtering off and taken up in a mixture of ethyl acetateand heptane to which aqueous ammonia had been added.

Two phases and a precipitate were obtained. The precipitate was filteredoff and then dried. The weight of this precipitate was 6.8 g.

This product was then purified on a column of silica gel.

The weight of pure product obtained was 4.1 g, corresponding to a yieldof 22.8%.

The characteristics of this product were:

Melting point (obtained by Mettler FP 89): M.p.=70° C. (solvent=acetone)

Elemental analysis: C₃₆ H₇₁ NO₅, M.W.=598

    ______________________________________                                                 C          H      N                                                  ______________________________________                                        Calculated 72.31        11.97  2.34                                           Theory     72.87        11.96  2.36                                           ______________________________________                                    

¹³ C NMR: conformed to the expected structure.

EXAMPLE 4

Preparation of hexadecyl 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate

The preparation was carried out as in Example 1, according to Process B,by mixing:

230 mmol (95 g) of potassium 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate,

230 mmol (69.9 g) of bromohexadecane,

1.9 g of trioctylmethylammonium chloride.

Irradiation lasted 4 minutes.

An amber liquid was obtained which congealed on cooling.

The solid obtained was finely divided, coarsened in water and filteredoff and then taken up in acetone, filtered off and dried.

85 g of product were thus obtained from the 137.5 g expected, i.e., ayield of 61.8%, the characteristics of which were:

Melting point (obtained by Mettler FP 89): M.p.=70° C. (solvent=acetone)

Elemental analysis: C₃₆ H₇₁ NO₅, M.W.=598

    ______________________________________                                                 C          H      N                                                  ______________________________________                                        Calculated 72.31        11.97  2.34                                           Theory     72.98        12.05  2.36                                           ______________________________________                                    

¹³ C NMR: conformed to the expected structure.

EXAMPLE 5

A comparative test was carried out on the effects of smoothing the hairof a cosmetic composition according to the invention, containing 1%hexadecyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate inisopropanol, with respect to a control consisting of isopropanol.

This test determined the coefficient of friction of hair by measuringthe force applied to a control mass in order to make it slide at aconstant rate over two hairs held tight in the same way. Measurement wascarried out by making the mass slide from the root towards the end ofthe hair (R→E) and vice versa (E→R).

    ______________________________________                                                      Coefficient of friction                                         Hair     Treatment  R → E                                                                             E → R                                   ______________________________________                                        Natural  Control    0.101 ± 0.003                                                                         0.127 ± 0.004                                        Composition                                                                              0.084 ± 0.003                                                                         0.116 ± 0.006                                        according to                                                                  the invention                                                        ______________________________________                                    

Application of the composition according to the invention resulted in amarked decrease in the coefficient of friction, in particular in theroot→end (R→E) direction, thus demonstrating an improvement in thesmoothing or disentangling of the hair.

EXAMPLE 6

A conditioner having the following composition was prepared:

hexadecyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate 0.2 g

Behenyltrimethylammonium chloride (at 80% in a 15/85 water/isopropanolmixture sold under the name of DC 80 by the Company Toho) 2 g

Water q.s. for 100 g

The solution was adjusted to a pH of 7.4.

After the various ingredients were mixed, a fluid milky solution wasobtained. This solution was applied to hair after a shampoo for a fewminutes and was then rinsed with water. Hair which can be more easilystyled was thus obtained.

EXAMPLE 7

A treating cream having the following composition was prepared:

    ______________________________________                                        Ceteareth-30 (according to the CTFA                                                                   2.5       g                                           nomenclature)                                                                 Hydroxyethyl cellulose  0.5       g                                           Behenyltrimethylammonium chloride (at 80%                                                             1.5       g                                           in a 15/85 water/isopropanol mixture sold                                     under the name of DL 80 by the Company Toho)                                  Hexadecyl 3-hydroxy-2- N-(hexadecyloxy-                                                               0.5       g                                           carbonyl)amino!propionate                                                     Water                   q.s. for 100                                                                            g                                           ______________________________________                                    

The solution was adjusted to pH 6.

After mixing, a white-coloured cream was obtained which was easilyapplied to hair and made it easy to disentangle.

EXAMPLE 8

The following cream shampoo was prepared:

    ______________________________________                                        Sodium lauryl ether sulphate, oxyethylenated                                                          8         g                                           with 2.2 mol                                                                  Coco-betaine (according to the CTFA                                                                   4         g                                           nomenclature)                                                                 Glycol distearate       1         g                                           Cocoyl diethanolamide   1         g                                           Hexadecyl 3-hydroxy-2- N-(hexadecyloxy-                                                               0.2       g                                           carbonyl)amino!propionate                                                     Preservative, dye, fragrance                                                                          q.s. for 100                                                                            g                                           and water:                                                                    ______________________________________                                    

The pH of the solution was adjusted to 7.5.

After mixing, an iridescent cream shampoo was obtained which wascomfortable on application, which had a gentle lather and which resultedin ease of disentangling and a smoothing effect to hair.

*: expressed as weight of active material in Examples 7 and 8.

What is claimed is:
 1. At least one racemic mixture of a serine compoundcorresponding to Formula I: ##STR4## wherein R and R', which areidentical or different, are selected from a linear or branchedhydrocarbon radical having from 8 to 30 carbon atoms, or the D-opticalisomer of Formula (I), or the L-optical isomer of Formula (I), or anon-racemic mixture of at least two of said optical isomers.
 2. The atleast one racemic mixture of a serine compound, the D-optical isomer,the L-optical isomer, or the non-racemic mixture of claim 1, wherein Rand R', which are identical or different, are saturated radicals orradicals which contain a double bond.
 3. The at least one racemicmixture of a serine compound, the D-optical isomer, the L-opticalisomer, or the non-racemic mixture of claim 1, wherein R and R', whichare identical or different, contain from 8 to 18 carbon atoms.
 4. Theserine compound according to claim 1, wherein said compound is selectedfrom:dodecyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate,octyl 3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate, hexadecyl3-hydroxy-2- N-(hexadecyloxycarbonyl)amino!propionate, dodecyl3-hydroxy-2- N-(2-ethylhexyloxycarbonyl)amino!propionate, octyl3-hydroxy-2- N-(2-ethylhexyloxycarbonyl)amino!propionate, hexadecyl3-hydroxy-2- N-(2-ethylhexyloxycarbonyl)amino!propionate, dodecyl3-hydroxy-2- N-(dodecyloxycarbonyl)amino!propionate, octyl 3-hydroxy-2-N-(dodecyloxycarbonyl)amino!propionate, hexadecyl 3-hydroxy-2-N-(dodecyloxycarbonyl)amino!propionate, dodecyl 3-hydroxy-2-N-(oleyloxycarbonyl)amino!propionate, octyl 3-hydroxy-2-N-(oleyloxycarbonyl)amino!propionate, and hexadecyl 3-hydroxy-2-N-(oleyloxycarbonyl)amino!propionate.
 5. The serine compound accordingto claim 4, wherein said compound is selected from:dodecyl 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate, octyl 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate, and hexadecyl 3-hydroxy-2-N-(hexadecyloxycarbonyl)amino!propionate.
 6. A process for thepreparation of the at least one racemic mixture of said serine compound,the D-optical isomer, the L-optical isomer, or the non-racemic mixtureof claim 1 comprising reacting, in the presence of a phase transferagent, at least one racemic mixture of an N-liposerine saltcorresponding to the formula: ##STR5## or the D-optical isomer ofFormula II, or the L-optical isomer of Formula II, or a non-racemicmixture of at least two of said optical isomers, with an activatedhydrocarbon derivative corresponding to the formula:

    R'X                                                        (III)

wherein R and R', which are identical or different, represent a linearor branched hydrocarbon radical having from 8 to 30 carbon atoms; Q⁺ isan organic or inorganic cation; and X is an activating group.
 7. Theprocess according to claim 6, wherein R and R', which are identical ordifferent, are saturated radicals or radicals which contain a doublebond.
 8. The process according to claim 6, wherein X is a halogen atomor a mesyloxy, brosyloxy or tosyloxy radical.
 9. The process accordingto claim 6, wherein said phase transfer agent is a solid/liquid phasetransfer agent.
 10. The process according to claim 9, wherein said phasetransfer agent is a quaternary ammonium compound.